Efficient Synthesis of Diaryl Quaternary Centers by Rh(II)/Xantphos Catalyzed Relay C-H Functionalization and Allylic Alkylation

A three-component reaction of N, N-disubstituted aniline, alpha-diazo ester, and an allylic electrophile has been realized by [Rh(II)](2)/Xantphos catalysis, providing a direct access to various aniline derivatives bearing diaryl allylic quaternary centers in good yields. The synthetic utility of this protocol was demonstrated by facile derivatization of the products for preparation of biologically relevant molecules and structural scaffolds, which offers a high potential for increasing the molecular diversity. Mechanistic studies identified alpha, alpha-diarylacetate species as an active intermediate, thereby revealing the presence of a C(sp(2))-H functionalization of aniline derivatives/allylic alkylation cascade in this attractive catalytic transformation.

Automated summary

A three-component reaction of N, N-disubstituted aniline, alpha-diazo ester, and an allylic electrophile has been achieved through [Rh(II)](2)/Xantphos catalysis, providing a direct access to diverse aniline derivatives with diaryl allylic quaternary centers in good yields. The synthetic utility of this method has been demonstrated by facile derivatization of the products, enabling the preparation of biologically relevant molecules and structural scaffolds, thereby offering a high potential for increasing molecular diversity. Mechanistic studies revealed the presence of a C(sp(2))-H functionalization of aniline derivatives/allylic alkylation cascade, with alpha, alpha-diarylacetate species identified as an active intermediate in this attractive catalytic transformation.